SG172553A1 - Graphite crucible and silicon single crystal manufacturing apparatus - Google Patents

Graphite crucible and silicon single crystal manufacturing apparatus Download PDF

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Publication number
SG172553A1
SG172553A1 SG2010089795A SG2010089795A SG172553A1 SG 172553 A1 SG172553 A1 SG 172553A1 SG 2010089795 A SG2010089795 A SG 2010089795A SG 2010089795 A SG2010089795 A SG 2010089795A SG 172553 A1 SG172553 A1 SG 172553A1
Authority
SG
Singapore
Prior art keywords
crucible
graphite crucible
gas
graphite
single crystal
Prior art date
Application number
SG2010089795A
Inventor
Hideo Kato
Hideaki Murakami
Mikio Suehiro
Original Assignee
Siltronic Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siltronic Ag filed Critical Siltronic Ag
Publication of SG172553A1 publication Critical patent/SG172553A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10Crucibles or containers for supporting the melt
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10Crucibles or containers for supporting the melt
    • C30B15/12Double crucible methods
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B35/00Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002Crucibles or containers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10Apparatus
    • Y10T117/1024Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1032Seed pulling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10Apparatus
    • Y10T117/1024Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1032Seed pulling
    • Y10T117/1052Seed pulling including a sectioned crucible [e.g., double crucible, baffle]

Abstract

Graphite Crucible and Silicon Single Crystal Manufacturing Apparatus AbstractTo provide a graphite crucible for silicon single crystal manufacturing according to the Czochralski method, wherein the graphite crucible has a long life cycle. A characteristic resides in that at least one gas venting hole is provided in a corner portion of the crucible. A gas generated by a reaction between the graphite crucible and a quartz crucible is released to the outside through said at least one gas venting hole. Thereby, formation ofSiC on the surface of the graphite crucible and deformation of the quartz crucible caused by the pressure of the gas are prevented.Fig. 1

Description

Graphite Crucible and Silicon Single Crystal Manufacturing
Apparatus
The present invention relates to a graphite crucible
Bb used in the manufacturing of a silicon single crystal according to the Czochralski method. It further relates to a silicon single crystal manufacturing apparatus according to the Czochralski method, comprising sald graphite crucible.
As one method for growing silicon single crystals, pulling methods represented by the Czochralski method (CL method) have been generally used. Normally, an apparatus used therein has a quartz crucible for retaining raw material silicon melt, wherein the crucible is surrounded by a graphite crucible having an Inner shape that serves to suppert the guartz crucible and to achieve uniform heating, and wherein a heater for heating is arranged outside thereof. Usually, the shapes of bcth the quartz crucible and the graphite crucible consist of a side wall having an approximately cylindrical shape and an appropriately radially chamfered bottom portion.
In the CZ method, a =zilicon raw material placed in the guartz crucible 1s heated and melted. Since the melting point of gilicon is about 1420°C, heating has to be carried cut so as to reach the melting peint at first. In such a case, the temperature of the heater has to be increased to about 1700°C. Due to this heating, both the graphite crucible and The quartz crucible are heated to the melting point of silicon or higher. When quartz exceeds about 1200°C, it begins to soften and deform, and, due to the load of the molten silicon in the quartz crucible, the quartz crucible almost entirely comes inte close contact with the inner shape of the graphite crucible supporting the quartz crucible from the outside. Along with a recent increase in the diameter of silicon wafers, an increase in the diameter and capacity of guartz crucibles is required in the CZ method as well, and it is becoming more important to control the temperature range and heating uniformity of the above described heating.
As shown in the equations below, a known problem of the CZ method is that, at the silicon melting temperature, a reaction 1s generated on the inner surface of the quartz crucible between $102, which is a component of the quartz crucible, and the molten silicon Si. As a result, a 8i0 gas 1s generated. Furthermore, also outside of the quartz crucible, this S10 gas reacts with the cuter surface of the graphite member, thereby forming a SiC solid. Moreover, on the outer surface of the quartz crucible, a $5i0 gas and a
CO gas are generated by a reaction betwean the cuter surface of the guartz crucible and the inner surface of the graphite crucible, and further, a SiC solid is formed by ancther reaction with the inner surface of the graphite crucible. The formed SiC has a thermal expansion coefficient significantly different from that of graphite.
Therefore, SiC becomes a cause of cracks, etc. during the cooling/heating cycle of the graphite crucible, thus limiting its service life in terms of safety, etc.
Moreover, as a result, the generated CC gas applies a pressure to the quartz crucible, causing it to deform.
Si02+81=8i0
S102+C=S1C+C0O
S10+2C=81iC+C0O
Several technligues regarding the improvement of the graphite crucible in order to solve the above problems are known. One cf them is a method disclosed in Japanese
Patent Application Laid Open No. ©61~44791, in which the CO gas generated between the quartz crucible and the graphite crucible 1s discharged by flowing an inert gas such as argon in a downstream direction between the guartz crucible and the graphite crucible and discharging the gas through the heles which are provided with a downward direction in a lower part of the side surface of the graphite crucible.
Moreover, a technigue in which horizontal holes are provided in the graphite crucible at positions above the liquid level of the molten silicon in order fo prevent deformation of the quartz crucible caused by the generated gas is disclosed in Japanese Patent Application Laid Open
No, 10-287992. Furthermore, a method in which the CO gas generated between the quartz crucible and the graphite crucible is discharged by flowing an inert gas such as argon in a downstream direction toward a bottom portion of the crucible along gas guiding grooves which are provided vertically on the inner surface of the graphite crucible and discharging the gas from the bottom portion is disclosed in Japanese Patent Application Laid Open No. 2008-201619.
However, 1t has begun to be recognized that these conventional methods are no longer adequate for the large diameter/large-capacity (high weight) quartz crucibles which are, particularly recently, used in the CZ method.
More specifically, providing complicated structures, such as gas gulding grooves, on the inner surface of the graphite crucible in order to discharge the generated gas is not preferred in terms of safe retention of the large- capacity (high weight) quartz crucible. Moreover, when a guartz crucible having a large diameter/large capacity (high weight) 1s used, the quartz crucible softened due to the high heating temperature deforms so that it almost entirely comes into close contact with the graphite crucible supporting it. Thus, it becomes difficult to provide a sufficient gas flow between said crucibles.
Therefore, novel graphite crucible technologies which prevent accumulation of pressure on the guartz crucible by smoothly discharging the generated CO gas and also prevent formation/accumulation of SiC on the inside of the graphite crucible, both without (i) providing a complicated structure on the inner surface of the graphite crucible and without (ii) providing a sufficient inert gas flow between the graphite crucible and the quartz crucible, are expected.
The present inventors have diligently carried out research in order to develop a graphite crucible that satisfies sald expectations. As a result, the inventors succeeded in finding a novel graphite crucible in which at least one approximately horizontal gas venting hole is provided at at least one particular position on the graphite crucible, due to which pressure does not accumulate on the surface of the guartz crucible thanks to a smooth discharge of the generated CO gas, and formation/accumulation of SiC on the inside of the graphite crucible is prevented. Thus, the present invention is accompliished.
Specifically, the pressnt invention relates to a graphite crucible used in the manufacturing of a silicon single crystal according to the Czochralski method, characterized in that at least one gas venting hole is provided in a corner portion of the graphite crucible.
The present invention also relates to the graphite crucible characterized in that the direction of the at least one gas venting hole is approximately horizontal. 5 The present invention further relates to a silicon single crystal manufacturing apparatus according to the
Czochralski method, characterized in that it comprises the graphite crucible of the present invention.
Here, the graphite crucible of the present invention includes net only the divided type but also the one-piece type. Furthermore, the present invention also includes a crucible made of CFC composite (carbon fibers reinforced carbon).
In the graphite crucible according to the present invention, the at least one gas venting hole is provided in the corner portion of the crucible. Therefore, sald graphite crucible is capable of smcothly releasing the gas generated by the reacticn between the guartz crucible and the graphite crucible, thereby preventing formation of SiC on the surface of the graphite crucible and deformation of the quartz crucible caused by the gas pressure. Since the silicon single crystal manufacturing apparatus according to 256 the Czochralski method of the present invention comprises the graphite crucible according to the present invention, during silicon single crystal manufacturing, the gas generated by the reaction between the guartz crucible and the graphite crucible can be smoothly released. Thereby, formation of 8iC on the surface of the graphite crucible and deformation of the quartz crucible caused by the gas pressure can be prevented, ensuring safety in manufacturing, and extending the life cycle of the graphite crucible.
FIG. 1 shows a graphite crucible of the present invention.
FIG. 2 is a drawing explaining the effects of gas venting holes of the present invention.
As lliustrated by an example of a graphite crucible 1 of the present invention shown in FIG. 1, in the graphite crucible of the present invention, a (inner) side portion 2 usually has an approximately perpendicular cylindrical shape and a bottom portion 3 an appropriately radially chamfered shape. A characteristic of said graphite crucible resides in that gas venting holes 5 are provided in a corner portion 4 thereof. Here, the graphite crucible 1 may be basically the same as conventionally publicly known graphite crucibles used in the manufacturing of silicon single crystals according to the Czochralski method, and there are no particular limitations imposed on whether said graphite crucible is a divided type or an one- piece type, and no particular limitations regarding its size, shape, or material. The crucible regarded as one unit has the above-explained shape during usage, even in the case of the conventionally publicly known divided type, where the crucible is divided into two or three parts.
Here, the corner portion of the graphite crucible of the present invention means the part (region) connecting the side portion and the bottom porticn. The graphite crucible cf the present invention has a function of supporting a major load cof a quartz crucible and molten silicon with its corner portien during usage. Since the quartz crucible is heated during usage to about its softening point, the guartz crucible is caused to be in a state in which it almost entirely comes into close contact with the graphite crucible at the bettom portion and the corner portion, and a desired heating effect is achieved. The gas venting holes 5 are provided as approximately horizontal holes in sald corner portion from inside to outside of the graphite crucible.
As schematically shown in FIG. 2, during usage, an inert gas 21 (usually argon gas) 1s, usually under reduced pressure, flowed outside of the graphite crucible and discharged. Therefore, the pressure of the inside 26 of the gas venting holes 25 and the gap 28 is at a state in which it 1s somewhat lower than the outside pressure 27 of the graphite crucible. Thus, as explained above, a CO gas is formed during usage due to the reacticn between a Si0 gas and C of the surface of the graphite crucible during the short period of time until said SiC gas reaches the gas venting holes. However, the gas 1s quickly discharged from the gas venting holes, and accumulation of pressure applied to the quartz crucible can be prevented. Therefores, the reaction of 31C and the surface cof the graphite crucible mainly takes place in the gas venting holes or in their outside peripheries alone.
In the present invention, the positions, shapes, number, and directions of the gas venting hcles provided in 256 the corner portion are not particularly limited, as long as the above-explained work-effect 1s carried out sufficiently. On the other hand, since the graphite crucible has to safely support the load of the quartz crucible and the molten silicon, in comprehensive consideration of the above, the positions, shapes, number, and directions of the gas venting holes can be selected to be in a preferred range. Particularly, regarding the directions of the gas venting holes, it is preferable to provide gas venting holes with a horizontal direction in order to more smoothly discharge the generated CO gas in a case when the interior of the furnace is filled with an inert gas such as argon.
Specifically, when a plurality of gas venting holes is provided, the positions therecf are preferred to be positions that equally divide the cylindrical corner portion. In the case of egually dividing positions, the decrease of crucible strength caused by the holes can be minimized. The shapes of the gas venting holes are not particularly limited, and circular shapes and polygonal shapes can be employed. The cross sectional areas thereof are also not particularly limited. However, the cross sectional area can be selected in sufficient consideration of how the quartz wall of the quartz crucible heated to about its softening point can be prevented from deforming : in the directions of the gas venting holes. Therefore, in comprehensive consideration thereof, the cross sectional area ¢f each gas venting hele is preferred to be 225 mmZ2 or a0 less. This means that, if the cross section is circular, the radius thereof is preferred to be in the range of 5 mm to 8 mm. When gas venting holes having this cross sectional area are employed, the number of the gas venting holes is preferably in the range of 2 te 3/crucible with division, and 6 to 8/crucible without division.
The directions of the gas venting holes are not particularily limited. However, the gas venting holes are preferred to be provided in directions with which the above-explained process, in cther words, the smooth discharging of the CO gas generated between the quartz crucible and the graphite crucible, can be carried out.
Specifically, providing sald gas venting holes approximately horizontally or somewhat upwardly is preferred since it brings aboul a smooth gas flow.
A silicon single crystal manufacturing apparatus 8 according to the Czochralski method of the present invention 1s characterized in that it comprises the above- explained graphite crucible of the present invention instead of a graphite crucible used in a conventionally publicly known apparatus. Thus, under conventionally publicly known manufacturing conditions, the CO gas generated between the quartz crucible and the graphite crucible is quickly discharged from the gas venting holes of the graphite crucible to the ocutside. As a result, formation and accumulation of SiC on the inside of the graphite crucible can be suppressed, and deformation of the quartz crucible due to the accumulated pressure of the CO gas ¢an be suppressed.
Example 50 Silicon ingots were pulled up by using the graphite crucible having an outer diameter of 500 mm and an inner diameter of 460 mm having holes of an inner diameter of &§ mm were horizontally provided egually at six locatiens in the corner portion. Any deposition of SiC on the inside of the crucible could not be confirmed at all. However, in the peripheries of the holes on the outside of the crucible, SiC deposition of about 3 mm was confirmed.
Furthermore, deformation of the guartz crucible due to CC gas was not cbserved at all.
The graphite crucible according to the present invention can be utilized in silicon single crystal manufacturing apparatuses according to the Czochralski method.

Claims (3)

Claims:
1. A graphite crucible used in the manufacturing of a silicon single crystal according to the Czochralski method, characterized in that at least one gas venting hole is provided in a corner portion of the graphite crucible.
2. The graphite crucible according to claim 1, characterized in that the direction of the at least one gas venting hole is approximately horizontal.
3. A silicon single crystal manufacturing apparatus according to the Czochralski method, comprising the graphite crucible according to claim 1 or 2.
SG2010089795A 2009-12-11 2010-12-06 Graphite crucible and silicon single crystal manufacturing apparatus SG172553A1 (en)

Applications Claiming Priority (1)

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JP2009281808A JP4918130B2 (en) 2009-12-11 2009-12-11 Graphite crucible and silicon single crystal manufacturing equipment

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SG172553A1 true SG172553A1 (en) 2011-07-28

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US (1) US8992682B2 (en)
EP (1) EP2336396B1 (en)
JP (1) JP4918130B2 (en)
KR (1) KR101297473B1 (en)
CN (1) CN102094235B (en)
SG (1) SG172553A1 (en)
TW (1) TWI439582B (en)

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CN102719881A (en) * 2012-07-06 2012-10-10 乐山新天源太阳能科技有限公司 Graphite crucible for single crystal furnace
KR101494531B1 (en) * 2013-06-27 2015-02-17 웅진에너지 주식회사 Crucible for Ingot glower
US10724150B2 (en) 2015-11-13 2020-07-28 Sumco Corporation Method of manufacturing silicon single crystal
CN106894079A (en) * 2015-12-21 2017-06-27 上海超硅半导体有限公司 Monocrystal silicon grower
CN106012000A (en) * 2016-08-11 2016-10-12 内蒙古中环光伏材料有限公司 Crucible apparatus used for silicon material production
CN106119959A (en) * 2016-08-30 2016-11-16 常熟华融太阳能新型材料有限公司 A kind of quartz ceramic crucible for polycrystalline silicon ingot casting
KR102237292B1 (en) 2019-07-31 2021-04-06 에스케이실트론 주식회사 Crucible for ingot grower
JP7192745B2 (en) * 2019-11-11 2022-12-20 株式会社Sumco Carbon crucible
CN110923805B (en) * 2020-01-09 2021-12-21 包头美科硅能源有限公司 Method for prolonging service life of quartz crucible for RCZ
CN113046824B (en) * 2021-03-23 2022-01-07 湖南世鑫新材料有限公司 Crucible system for pulling up single crystal silicon
CN115522257A (en) * 2021-06-25 2022-12-27 上海超硅半导体股份有限公司 Crystal growth graphite crucible for integrated circuit
CN115522256A (en) * 2021-06-25 2022-12-27 上海超硅半导体股份有限公司 Method for processing crystal growth graphite crucible for integrated circuit
WO2023230243A1 (en) * 2022-05-25 2023-11-30 Luxium Solutions, Llc Enclosed crystal growth

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Publication number Publication date
EP2336396A1 (en) 2011-06-22
JP2011121827A (en) 2011-06-23
US20110139064A1 (en) 2011-06-16
CN102094235A (en) 2011-06-15
JP4918130B2 (en) 2012-04-18
CN102094235B (en) 2014-08-20
TWI439582B (en) 2014-06-01
US8992682B2 (en) 2015-03-31
KR101297473B1 (en) 2013-08-16
KR20110066850A (en) 2011-06-17
TW201120257A (en) 2011-06-16
EP2336396B1 (en) 2012-07-04

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